Incorporable photoinitiator

• US 20050228062A1
• Filed: 04/17/2003
• Published: 10/13/2005
• Est. Priority Date: 04/26/2002
• Status: Active Grant

• Current Assignee: IGM Group B.V.
• Original Assignee: BASF SE
• Inventors: Wolf, Jean-Pierre, Peter, Wolfgang, Husler, Rinaldo, Sommerlade, Reinhard H., Boulmaaz, Souad
• Granted Patent: US 7,588,880 B2
• Time in Patent Office: Days
• US Class Current: 522/6
• CPC Class Codes: C08F 2/50 with sensitising agents

Abstract

Compounds of formula (I), wherein Y is, for example, C₃-C,₁₂alkylene, butenylene, butynylene, or C₄-C,₁₂alkylene interrupted one or more times by non-consecutive —O— or —NR₂—; R₁ is a reactive group selected from OH, SH, NR₃R₄, —(CO)—OH, —(CO)—NH₂, SO₃H, —C(R₅)═CR₆R₇, oxiranyl, —O—(CO)—NH—R₈—NCO and —O—(CO)—R₉—(CO)—X; R₂ is hydrogen, C₁-C₄alkyl or C₂-C₄ hydroxyalkyl; R₃ and R₄ are each independently of the other hydrogen, C₁-C₄alkyl or C₂-C₄hydroxyalkyl; R₅, R₆ and R₇ are each independently of the others hydrogen or methyl; R₈ is, for example, linear or branched C₄-C₁₂alkylene, or phenylene; R₉ is, for example, linear branched C₁-C₁₆alkylene, —CH═CH—, —CH═CH—CH₂—, C₆-cycloalkylene, phenylene or naphthylene; and X, X₁ and X₂ are each independently of the others OH, Cl, OCH₃ or OC₂H₅; are suitable as photoinitiators that can be incorporated in a formulation to be cured.

Claims

1. An incorporable photoinitiator compound of formula I

2. An incorporable photoinitiator compound of formula I according to claim 1 wherein Y is —

CH₂—

CH(CH₃)—

, -n-propylene, —

CH₂C(CH₃)₂CH₂—

, hexylene, —

CH₂CH₂—

O—

CH₂CH₂—

, —

(CH₂CH₂—

O)₂CH₂CH₂—

,

3. An incorporable photoinitiator compound of formula I according to claim 1 wherein R₁ is OH.

4. An incorporable photoinitiator of formula I according to claim 1 wherein

Y is C₄-C₁₂alkylene interrupted one or more times by non-consecutive —

O—

;

R₁ is a reactive group selected from OH, oxiranyl and —

O—

(CO)—

NH—

R₈—

NCO; and

5. A process for the preparation of a compound of formula I according to claim 1 wherein R₁ is OH, which process comprises

reacting a phenylglyoxylic acid monoester II

wherein

R is C₁-C₄alkyl,

with a diol III

HO—

Y—

OH  

 

(III), wherein

Y is as defined in claim 1,

wherein there is used as catalyst lithium acetate, sodium acetate, potassium acetate, magnesium acetate, barium acetate, zinc acetate, cadmium acetate, copper(II) acetate, cobalt(II) acetate, aluminium acetate, calcium oxide, lithium methanolate, sodium methanolate, titanium tetraisopropanolate, aluminium triisopropanolate, lithium tert-butanolate, 4-(dimethylamino)pyridine or dibutyltin diacetate.

6. A process according to claim 5 wherein lithium acetate is used as the catalyst.

7. A process according to claim 5 wherein the reaction is carried out at temperatures of from 20°

C. to 180°

C.

8. A process according to claim 4 wherein the amount of catalyst is from 0.1 to 20 mol %, based on the glyoxylic ester component of formula (II).

10. A process for the preparation of an incorporable photoinitiator of formula I according to claim 1, which process comprises

reacting a compound of formula I according to claim 1 wherein R₁ is OH with an isocyanate, a carbamoyl chloride, a thioisocyanate, an acid chloride, an acid ester, an acid anhydride, a chloroformate or epichlorohydrin.

11. A photopolymerizable composition comprising

(a) at least one ethylenically unsaturated photopolymerisable compound and

(b) as photoinitiator, at least one compound of formula I according to claim 1.

12. A composition according to claim 11 comprising, in addition to component (b), also further initiators (c) and/or additives (d).

13. A composition according to claim 12 wherein the additional photoinitiators (c) are compounds selected from the group consisting of formulae VIII, IX, X, XI and XII

14. A composition according to claim 13 wherein

R₂₅ is hydrogen, —

OCH₂CH₂—

OR₂₉, morpholino, SCH₃ or a group

R₂₆ is hydroxy, C₁-C₁₆alkoxy, morpholino or dimethylamino;

R₂₇ and R₂₈ are each independently of the other C₁-C₄alkyl, allyl, phenyl, benzyl or C₁-C₁₆alkoxy, or R₂₇ and R₂₈, together with the carbon atom to which they are bonded, form a cyclohexyl ring;

R₂₉ is hydrogen or

R₃₀, R₃₁ and R₃₂ are hydrogen;

R₃₃ is C₁-C₁₂alkyl, unsubstituted phenyl or phenyl substituted by C₁-C₁₂alkyl or/and by C₁-C₁₂alkoxy;

R₃₄ is

R₃₅ is phenyl, which is substituted by one or more C₁-C₄alkyl or/and C₁-C₄alkoxy substituents.

15. A composition according to claim 11, containing from 0.05 to 20% by weight of the photoinitiator component (b).

16. A composition according to claim 11 that, in addition to comprising the photochemically curing component, also contains a thermally curable component.

18. A process for the photopolymerization of a non-volatile monomeric, oligomeric or polymeric compound containing at least one ethylenically unsaturated double bond, wherein a composition according to claim 11 is irradiated with light in the range from 200 to 600 nm.

20. A process according to claim 18 for the preparation of pigmented and unpigmented surface-coating compositions, printing inks, screen printing inks, offset printing inks, flexographic printing inks, powder coatings, printing plates, adhesives, dental compositions, optical waveguides, optical switches, color test systems, composite materials, glass fiber cable coatings, screen printing stencils, resist materials, color filters, gel coats (thin layers), in the encapsulation of electrical and electronic components, in the production of magnetic recording materials, of three-dimensional objects by means of stereolithography, of photographic reproductions, image-recording material, oholographic recordings, in the production of decolorising materials, decolorising materials for image-recording materials, or in the production of image-recording materials using microcapsules.

21. A coated substrate that is coated on at least one surface with a composition according to claim 11.

22. A process for the photographic production of relief images in which a coated substrate according to claim 21 is exposed imagewise and then the unexposed portions are removed using a solvent.

23. A composition according to claim 13, containing from 0.05 to 20% by weight of photoinitiator components (b)+(c).

9. (canceled)

17. (canceled)

19. (canceled)